Polycondensation products of phosphoric acid amides with aliphatic polyethers as developer adjuvants



United States Patent 3,346,386 POLYCONDENSATION PRODUCTS 01? PHOS-PHORIC ACID AMIDES WITH ALlPHATIC POLYETHERS AS DEVELOPER ADJUVANTSHerbert Miiller, Leverkusen, HerbertGrabhijfer, Cologne- Flittard, HansUlricli, Leverkusen, and Rolf-Fred Posse, Cologne-Flittard, Germany,assignors to Agfa Aktiengesellschaft, Leverkusen, Germany, a corporationof Germany No Drawing. Filed Dec. 10, 1963, Ser. No. 329,364 Claimspriority, application Germany, Dec. 17, 1962,

A 41,899 Claims. (Cl. 96-66.3)

The invention relates, to a process for the production of photographicimages, the development of the exposed photographic material beingcarried out in the presence of polycondensation products of phosphoricacid amide derivatives with aliphatic polyethers. Phototechnical filmsof the co called lithoor line-type are increasingly being used in thereprography, in particular photo production of screened photographicprints. Lithoor line films. are such films which can be developed indeveloper c0mpositions containing formaldehyde bisulfite compounds tovery high 'y-values and thus to sharp screened dots. The term 'y is tobe understood the tangent of the angle between the straight-line portionof the characteristic curve (or H and D curve) of the leg E axis.

It is true that processing of such films with formaldehyde-containingdevelopers leads to excellent results, but the operation must beperformed with great care, since the period during the development whichyields a sharp screen dot, i.e., steepest gradation, is too brief,approximately between half and 1 /2 minutes.

It is known to add phosphorylated alkylene oxide derivatives tophotographic silver halide emulsions to improve the mechanicalproperties. Such compounds are,

however, not operative for producing a steep gradation.

It is an object of the present invention to provide novel compoundsWhich are added to the photographic layers or to the aqueous developingcomposition and with which an extremely high v-value can be obtainedupon development. A further object is to provide compounds whichsimultaneously effect the development in such a manner that the periodof time during which that high *y-value is obtained can be extended sothat the development is more convenient and simpler. Other objects, someof which are referred to specifically hereinafter will be. evident tothose skilled in the art to which this invention pertains.

These objects have been achieved by providing condensation products ofaliphatic polyethers with terminal hydroxy groups and phosphoric acidamide derivatives of the formula in which R represents an alkyl grouppreferably with up to 5 carbon atoms or an aryl, preferably phenyl oralkyl phenyl, or aralkyl, such as benzyl group; R can have the samemeaning as R or can represent a hydrogen atom and X represents halogenatoms such as bromine or preferably chlorine, or alkoxy groups,preferably short-chain groups having up to 5 carbon atoms such asmethoxy and ethoxy; R and R can be together the methylene groups to forma heterocyclic rin in particular a piperidine or pyrrolidine ring.

Especially suitable polyethers are polyethylenglycols which contain atleast 3, preferably 410 CH CH .O- units.

3,346,386 Pa ented s 0, 1.86.7

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polyether are advantageously reacted with, 1 mol Qf theamido phosphoricacid compound. The following amide p sp o ic d omp ds i pa i u a u li CHNHPOCI C H NHPOCl C H NH-POCI C H NHPOCl s s iP 12 4-ClC H NHPOCl2-,4'-Cl;C H N'HPOCl & a)a s '2NH C 2 CH NPOCI 0 1a, ,NPocr(CgHgJgNPOBI'z lSO-C4H9) a n sNPOC i (Cs 5) 2 5 PQC z 6 5)2 C 2 5H10 C 2I cnannrow i oi 2H5 H C2H5J2 CSH'LNHPO(OC2H5)V2 $Q'-C4H9 H 2 5)2C6H5NHPO(OCH3)2 sH5 .HP (Q 2 5)2 CsHsNHPO( CsH'i-is9.)2 2.,4-CI CGH3NHPto nail -Q aCs 4 H (Q 2H5)-a H3)2 (OC T )2 2 s)2NP (-Q Ha). a '1)2NPgH5)a (C4 9).2 Q( C4 9.) 2- (Cs s) z P' z sh The aforesaid compounds aredescribed, for example, in the article by A. Michaelis, Ann. volume 326,129 1903 The products which are obtained by reaction of the abovecomponents and which are generally water-soluble, probably have thefollowing structure:

HO lCHz-QHz-O) the integers n, m and Z have the following meaning;

m=0 or at least 3, preferably 4-10; n=at least 3, preferably 4--10; .=lt: s 1, pre e ab y .400

The action of these compounds in connection with lithe development wasall the more unexpected because shortchain polyethylene glycols such asoctaethylene glycol and even the analogous phosphoric and phosphorousacid polyethylenglycol ester, as described in Belgian Patent 609,497, donot produce any sharp gradations. By the term lithe development or lithodeveloper we intend a development process which yields images with verysteep gradation of at least 3 by the use of a developer which contains aformaldehyde-bisulfite compound.

Suitable for the process according to the invention are all silverhalide emulsions which show a sufiiciently high gradation effect withdevelopers which contain formaldehyde.

The silver salts in such least 50 mol percent of according sions, the

emulsions ge e av com rise at i e ch or de Pe the pros s to theinvention, it is preferred to use ernnl-t silver halide of whichcontains at least 65 mol percent of silver chloride and 35 mol percentor less silver in the emulsion. It is advantageous to use from 10 to100' mg. per mol of silver halide. The compounds are added to thedeveloper solutions or to the emulsions, advantageously in quantities of30 to 300 mg./ liter of the emulsion-casting solution. The final driedsilver halide emulsion layer with such addition accordingly containsbetween 0.5 and 10 mgrof the compound per squarc meter.

By the addition of the phosphoric acid amide esters of the presentinvention to the emulsion or to the developer,

the ry-value in the development is shifted from about 6 to 8 to 15;Moreover, the period of development time during which the steepestgradation or screen dot sharpness is produced is raised from about 1minute to 3 to 4 minutes. An additional advantage is that a developercontaining formaldehyde is much less dependent'upon temperature when ithas such an additive. Whereas a developer *without this additive reactswith a considerable development acceleration and thus a pronouncedshortening of the development time when the temperature is raised by 1to 2, good results are obtained with a developer temperature between 15and 40 when phosphoric acid amide esters are added. Because of thelonger processing period, the advantages described above lead to muchmore reliable Working. The compounds according to the invention canbe'added to the developer composition in an amount of 0.01 to 10 gramsper liter of the aqueous composition.

The phosphoric acid amide esters according to the invention are preparedby conventional esterification methods; the degree of condensation ofthe ester can be influenced as required by variations in the reactiontime and in the reaction temperature. The higher the temperature, thehigher is the. degree of condensation of the phosphoric acid amideesters, in particular the integer'Z" of the polyether ester formula canbe influenced by varying the temperature. Thus, compounds were obtainedin which Z had a value of about 100, 300, 800 or 1000. The degree' ofcondensation can further. be influenced, in particular the integer ,Zreferred to hereinbefore, by varying the proportion of the startingcompounds for theconden'sation. Compounds with a very high value of Zhaving rechain are obtained if the phosphoric acid amide reactant andthe aliphatic polyether are reacted in a molar ,proportion of 1:1;Compounds containing only 1 phosphoric acid amide grouping are obtainedif the phosphoric acid amide reactant and the polyether are reacted inamolar proportion of 1:2. Y

r In the following examples concerned with production, a number ofcondensation products are separately described:

' COMPOUND I 19 g. of N,N-diethylphosphoric acid amide-dichloride V areadded in portions at temperatures between and with methylene chloride.After drying with potash, the

methylene chloride is completely evaporated. There are obtained 39 g. ofa syrupy amber-coloured substance.

COMPOUND II 41.2 g. of nonaethylene glycol, 31.2 g. of pyridine and 19g.of N,N-diethyl phosphoric acid amidedichloride are reacted and worked upin the manner described above.

There are obtained 45 g. of a semi-solid, brown-coloured substance,which is diluted with water to a 10% solution and purified withactivated carbon.

'COMPOUND III The preparation is similar to that of compound (I), byreaction of 28.2 g.'of hexaethylene glycol, 31.2 g. of pyridine and 22.4g. of N-methyl-N-phenyl phosphoric acid amide dichloride. There areobtained 39 g. of a browncoloured, semi-solid substance, which ispurified with activated carbon.

COMPOUND IV 41.4 g. of nonaethylene glycol, 31.2 'g. of pyridine and22.4 g. of N-methyl-N-phenyl phosphoric acid amidedichloride are reactedin a manner analogous to Compound 'I. There are formed 50 g. of'abrown-coloured semi-solid substance, which is diluted with water anddecolourised with activated carbon.

COMPOUND, v

1 mol of propylamidophosphoric acid diethyl ester is heated withapproximately a 10% molar excess of octapeating phosphoric acid amideunits in a wholly ether Grams Anhydrous sodium sulphite 30 Boric acid7.5 Hydroquinone I 7 2 2.5

Potassium metabisulphite 2.5

P araformaldehyde 7.5

I Potassium bromide 1.5

ethylene glycol in the presence of'reesterification catalysts, such assodium or sodium'alcoholate, for several hours at 100 to 120 C. Theethyl alcohol that is liberated is constantly distilled 01? in vacuo andthe residue can be used I for the purpose of the present invention.

Example 1 A'gelatino-silver halide emulsion with 15 mol percent of AgBrand of AgCl is washed, ripened to the maximum sensitivity and, afteradding 4-hydroxy-6-methyl- 1,3,3a,7-tetrazaindol or other stabilisersand a Wetting agent, cast onto a suitable film support; 7

Other film strips are prepared with the use of the same emulsions, 80mg. of octaethylene glycol or 80 mg. of the Made up with water to 1litre.

' In the sensitometric evaluation of the film strips, the followingresults are obtained:

Emulsion additive Gradation Fogging Octaethylene glyc0l 6 0. 04 Compoun7 15 7 I 0.04 Compound IL- 15 0. 04' Compound III. 15 0. 04 Compound IV15 0.04

Example 2 Film strips of the emulsion described in'Example 1 are exposedbehind a grey stepped wedge and are developed in the developer referredto above for periods from 1 to 6 minutes (Experiment A). The same filmspecimens, after addition of mg. of the Compound I (Experiment B) and100 mg. of the phosphorous acid glycol ester according to Example 1 ofBelgian Patent 609,497 (Experiment C), are developed in the samedeveloper. 1

Result A {Time Minutes. 1. 2 2. 5 3 4 5 6 'y-Value r 10 10 6 6 6 6 B{'Tirne, Minutes 1. 5 2 2. 5 3 4 5 6 v-value 8 10 10 10 10 10 8 C Time,Minutes. 1. 5 2 2. 5 3 4 5 6 7-value .1 10 10 10 8 6 6 6 Example 3 Anemulsion as in Example 1 is given the usual additives (wetting agents,stabilisers and hardeners) and is divided into three portions and castas follows onto a film support:

A: Without additive B: +80 mg. of the Compound 11 per mol of silverhalide -C: +80 nag. of the analogous phosphoric acid glycol esteraccording to Example 3 of Belgian Patent No. 609,497. Several samplesare cut from these webs and exposed in a sensitometer behind a greystepped wedge and developed as follows in the aforementioned developerat 18 C.:

A {Time Minutes 1. 5 2 2. 5 3 4 5 6 'y-value 10 10 10 6 6 6 6 B {Time,Minutes. 1. 5 2 2. 5 3 4 5 6 v-value 8 10 10 10 10 10 8 C )Tirne,Minutes 1. 5 2 2. 5 3 4 5 6 L'y-value 10 10 10 6 6 6 6 We clarm:

1. In a process for developing an exposed photographic materialcontaining at least 1 silver halide emulsion layer, the silver halide ofwhich contains at least 50 mol percent of silver chloride, in aphotographic aqueous developer composition containing formaldehyde, theimprovement which consists in developing the exposed photographicmaterial in contact with a reaction product of 1 to 2 mols of aliphaticpolyether having terminal hydroxy groups, and 1 mol of a phosphoric acidamide derivative of the formula 111 which R is a radical of the groupconsisting of alkyl, phenyl, alkyl phenyl and phenyl alkyl; R is asubstituent of the group consisting of hydrogen, alkyl, phenyl, alkylphenyl and phenyl alkyl or R and R together are the methylene groupsrequired to complete a heterocyclic radical of the group consisting ofpyrrolidino and piperidino and X represents a substituent of the groupconsisting of chlorine, bromine and lower alkoxy.

2. A process as defined in claim 1, in which the reaction products hasthe following formula:

R1 R2 Z wherein R and R have the meaning defined in claim 1, m can be 0and an integer from 3 to 10; n is an integer from 3 to 10 and Z is aninteger from 1 to 1000.

3. A process as defined in claim 1, wherein the reaction product has thefollowing formula 1|O-(CHz-CHz-O)n m N R1 R: Z

compound of the following formula 0 r l H HO-- CH2CII2O ]|?0(CH2-CH2-O)11 H R1 R2 Z wherein R and R have the meaning defined inclaim 1, m can be 0 and an integer from 3 to 10; n is an integer from 3to 10 and Z is an integer from 1 to 1000.

5. An aqueous composition containing a silver halide photographicdeveloper and from 0.01 to 10 grams per liter of a compound of thefollowing formula:

wherein R and R have the meaning defined in claim 1, m can be 0 and aninteger from 3 to 10; n is an integer from 3 to 10 and Z is an integerfrom 1 to 1000.

References Cited UNITED STATES PATENTS 3,156,718 11/1964 Lorenz et al.260-461 3,157,685 11/1964 Szabo et a1. 26046l 3,158,483 11/1964 Lowe etal. 9666 3,162,534 12/1964 Powers et al. 96-66 NORMAN G. TORCHIN,Primary Examiner. C. E. DAVIS, Assistant Examiner.

1. IN A PROCESS FOR DEVELOPING AN EXPOSED PHOTOGRAPHIC MATERIALCONTAINING AT LEAST 1 SILVER HALIDE EMULSION LAYER, THE SILVER HALIDE OFWHICH CONTAINS AT LEAST 50 MOL PERCENT OF SILVER CHLORIDE, IN APHOTOGRAPHIC AQUEOUS DEVELOPER COMPOSITION CONTAINING FORMALDEHYDE, THEIMPROVEMTN WHICH CONSISTS IN DEVELOPING THE EXPOSED PHOTOGRAPHICMATERIAL IN CONTACT WITH A REACTION PRODUCT OF 1 TO 2 MOLS OF ALIPHATICPOLYETHER HAVING TERMINAL HYDROXY GROUPS, AND 1 MOL OF A PHOSPHORIC ACIDAMIDE DERIVATIVE OF THE FORMULA